CN110106426B - Easily activated hydrogen storage alloy, method for producing same, and melting apparatus - Google Patents
Easily activated hydrogen storage alloy, method for producing same, and melting apparatus Download PDFInfo
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Abstract
The application discloses an easily activated hydrogen storage alloy, a manufacturing method thereof and smelting equipment, wherein the easily activated hydrogen storage alloy has a chemical general formula as follows: ti50‑xMxFe50‑yNy‑(TiFe)100‑ aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80. The hydrogen storage alloy can effectively store hydrogen density, hydrogen absorption and desorption rate, anti-pulverization, long cycle life and the like, and keeps the original performance advantages.
Description
Technical Field
The application relates to the technical field of hydrogen energy, in particular to an easily activated hydrogen storage alloy, a manufacturing method thereof and smelting equipment.
Background
The hydrogen energy is a future star in the field of energy, is called final energy by experts in the industry, has the advantages of wide hydrogen source, high combustion heat value, cleanness, no pollution, multiple utilization forms, good safety and the like, and is commercially applied to the fields of mobile equipment such as vehicles, ships, unmanned planes, aerospace and the like and the fields of mobile and fixed energy storage.
The storage of hydrogen energy is one of the bottlenecks in the development of the hydrogen energy industry. The hydrogen storage method comprises three methods of high-pressure gas, low-temperature liquid hydrogen, organic liquid and solid. At present, hydrogen fuel cell vehicles mainly pushed at home and abroad all apply a high-pressure gaseous storage technology, and the pressure is 35MPa and 70 MPa. The high-pressure hydrogen storage faces the problems of construction of a hydrogenation station, hydrogen pressurization cost, use safety of hydrogen in a closed environment and the like. Therefore, the high-pressure hydrogen storage technology still faces a plurality of bottleneck problems in domestic market popularization. The solid alloy hydrogen storage adopts a low-pressure hydrogenation technology, has a very mature application system, has high solid alloy hydrogen storage safety, large volume hydrogen storage density (2-3 times of high-pressure hydrogen storage), long cycle life (more than 5000 times of cycle charge and discharge, and covers the whole life cycle of various application scenes), and is suitable for scenes which are insensitive to weight and have higher requirements on safety, such as city passenger cars, heavy trucks, logistics vehicles, forklifts, scenic spot sightseeing vehicles, ships, hydrogen energy buildings and the like.
The common hydrogen storage alloy has ferrotitanium, nickel lanthanum, manganese titanium, magnesium, vanadium-based solid solution system and the like, integrates the performances of hydrogen storage density, cycle life, cost, use temperature and pressure, hydrogen charging and discharging rate, material pulverization, poison resistance and the like, and has more advantages than other hydrogen storage alloys, wherein the weight effective hydrogen storage density of the alloy material is more than or equal to 1.8wt% (hydrogen discharging cut-off pressure of 0.3MPa abs under the condition of 65 ℃), the volume hydrogen storage density is more than or equal to 120g/L, the 1000-week cycle attenuation rate is less than or equal to 10% (99.999% high-purity hydrogen cycle), the working temperature is-40-80 ℃, the working pressure is 0.1-4MPa abs, the hydrogen charging and discharging speed is high, and the hydrogen charging volume expansion rate of the alloy is 16-17% (good pulverization resistance). However, the titanium-iron hydrogen storage alloy has the problem of poor activation performance, and the alloy material needs to be inoculated and activated for a long time for several hours to dozens of hours at the temperature of 400 ℃ and in a high-purity hydrogen atmosphere of 4MPa, and even repeatedly charged and discharged for several times to dozens of times, so that the alloy material can absorb hydrogen. When the hydrogen storage tank is used, the environment with the high temperature of 400 ℃ is not suitable to be provided, and the problems of low production efficiency, high production cost, waste of equipment resource occupation and the like are caused by long-time inoculation activation and repeated hydrogen charging and discharging. Therefore, the improvement of the activation performance of the ferrotitanium hydrogen storage alloy is a key technology which needs to be mainly solved in the commercialization and the commercialization popularization of the material.
Heretofore, the commonly employed method for improving the activation properties of a titaniferous hydrogen storage alloy is alloying, i.e.: by adding transition metal elements such as V, Cr, Mn, Nb and Zr, rare earth elements such as La, Ce, Pr, Nd and Sm, and alkali metals or alkaline earth metals such as Li, Mg and Ca, Ti or Fe is partially replaced, and a ternary or multicomponent alloy taking TiFe as a matrix is formed. Although the method slightly improves the activation performance of the ferrotitanium hydrogen storage alloy, the activation condition still realizes low-cost and high-efficiency operation, and the method also has the problems of sacrificing the effective hydrogen storage density of the alloy, increasing alloy pulverization, influencing cycle life and the like, and has lower practical application value.
Therefore, the problem to be solved at present is to combine the engineering requirements of hydrogen storage tank products, take into account the comprehensive hydrogen storage performance of ferrotitanium hydrogen storage alloy from the material level, and solve the activation performance problem of the alloy, thereby improving the production efficiency of the hydrogen storage tank, reducing the production and manufacturing cost, and promoting the application and market popularization of the hydrogen storage tank in the fields of vehicles, ships, portable power supplies, hydrogen energy buildings, and the like.
Therefore, in order to overcome the drawbacks of the prior art, it is necessary to provide a hydrogen occluding alloy.
Disclosure of Invention
It is an object of the present application to overcome the above problems or to at least partially solve or mitigate the above problems.
According to one aspect of the present application, there is provided an easily activatable hydrogen storage alloy having the general chemical formula: ti50-xMxFe50-yNy-(TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80.
Preferably, the easily activatable hydrogen storage alloy comprises: the hydrogen storage alloy comprises a hydrogen storage alloy main body and a hydrogen storage material active agent arranged on the surface of the hydrogen storage alloy main body, wherein the chemical general formula of the hydrogen storage alloy main body is as follows: ti50-xMxFe50-yNyThe chemical general formula of the hydrogen storage material active agent is as follows: (TiFe)100-aAa。
Preferably, x is greater than 0 and less than or equal to 25, and M is one or more of V, Zr, Mg and Al.
Preferably, the weight of the hydrogen storage material active agent is 0.05% -1% of the weight of the hydrogen storage alloy main body.
According to an aspect of the present application, there is provided a method of manufacturing an easily activatable hydrogen storage alloy, comprising:
s1: the chemical formula of the preparation is Ti50-xMxFe50-yNyThe main body of the hydrogen storage alloy and the general formula of the preparation is (TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80;
s2: smelting the hydrogen storage alloy main body, and spraying the hydrogen storage material active agent to the surface of the molten hydrogen storage alloy main body to prepare an as-cast hydrogen storage alloy;
s3: and annealing the as-cast hydrogen storage alloy to obtain the easily-activated hydrogen storage alloy.
Preferably, in step S3, the as-cast hydrogen occluding alloy is annealed at a temperature of 1000 ℃ to 1400 ℃ for 0.5h to 4 h.
Preferably, the hydrogen storage alloy main body is smelted under the environment of vacuum or inert gas protection, and the hydrogen storage material active agent is sprayed to the surface of the molten hydrogen storage alloy main body within 5-180 seconds after the heating power supply is turned off, or the hydrogen storage material active agent is sprayed to the surface of the molten hydrogen storage alloy main body in the mold within 5-180 seconds after the mold casting and casting.
Preferably, the weight of the hydrogen storage material active agent is 0.05% -1% of the weight of the hydrogen storage alloy main body.
According to one aspect of the present application, there is provided a smelting apparatus for producing an easily-activatable hydrogen storage alloy, the smelting apparatus comprising:
the smelting furnace system comprises a smelting furnace, a mechanical arm, a crucible and a mold, wherein the mechanical arm penetrates through the wall of the smelting furnace and extends to the interior of the smelting furnace, and the crucible and the mold are arranged in the smelting furnace;
an activator system within the smelting furnace, comprising: the device comprises an active agent storage tank, an active agent conveying pipeline and an active agent injection gun which are sequentially communicated, wherein the mechanical arm is connected with the active agent injection gun;
the gas conveying system outside the smelting furnace comprises a tank part for bearing the conveying gas, and the tank part is communicated with the active agent storage tank through a pipeline.
Preferably, the height of the active agent storage tank is 200-400mm, the outer diameter of the active agent storage tank is 50-100mm, the pipe diameter of the active agent injection gun is 5-15mm, and the pipe diameter of the muzzle of the active agent injection gun is 0.1-1 mm.
The invention has the advantages that: (1) compared with ferrotitanium hydrogen storage alloy, the ferrotitanium hydrogen storage alloy is easy to activate, can be activated at one time under the conditions of lower temperature and hydrogen pressure, improves the activation efficiency of the hydrogen storage tank, saves hydrogen, reduces the human input, reduces the energy consumption, shortens the occupied time of production equipment and the like when the hydrogen storage alloy is applied in engineering, and greatly reduces the production cost of the hydrogen storage tank. (2) Compared with alloyed easy-to-activate ferrotitanium hydrogen storage alloy, the material has the advantages of effective hydrogen storage density, hydrogen absorption and desorption rate, pulverization resistance, cycle life and the like, and maintains the original performance advantages. (3) The improved smelting equipment is simple to operate and is suitable for various smelting modes. (4) The hydrogen storage alloy can be easily activated in a block state, so that the processes of crushing and pulverizing the hydrogen storage alloy are omitted, the production efficiency is improved, and the production cost of materials is reduced.
The above and other objects, advantages and features of the present application will become more apparent to those skilled in the art from the following detailed description of specific embodiments thereof, taken in conjunction with the accompanying drawings.
Drawings
Some specific embodiments of the present application will be described in detail hereinafter by way of illustration and not limitation with reference to the accompanying drawings. The same reference numbers in the drawings identify the same or similar elements or components. Those skilled in the art will appreciate that the drawings are not necessarily drawn to scale. In the drawings:
FIG. 1 is a schematic view of a smelting plant for producing an easily activated hydrogen storage alloy according to one embodiment of the present application;
FIG. 2 is a graph showing the hydrogen absorption kinetics of the easy-to-activate ferrotitanium-based hydrogen storage alloy prepared in example 7 of the present invention;
FIG. 3 is a hydrogen evolution pressure-composition-temperature (PCT) graph of a titanium-iron-based hydrogen storage alloy which is easy to activate and prepared by example 7 of the present invention;
FIG. 4 is a gold phase diagram of a ferrotitanium-based hydrogen storage alloy that is readily activated and is produced in accordance with practice 7 of the present invention;
FIG. 5 is a flow chart of a method of making an easily activatable hydrogen storage alloy in accordance with an embodiment of the present invention.
The reference numbers in the figures mean: 1, smelting a furnace; 11 a mechanical arm; 12 an observation window; 13 a crucible; 14, a mould; 2, an active agent storage tank; 21 an active agent delivery conduit; 22 an active agent spray gun; 3, an argon tank; 31 an argon gas pipe; an argon valve; a-bulk phase region of a ferrotitanium-based hydrogen storage alloy; b-active agent phase region.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth, such as medium-and long-term load prediction methods, techniques based on user energy characteristics, in order to provide a thorough understanding of the embodiments of the invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known user energy characteristic-based medium and long term load prediction methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
In addition, in order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the specific embodiments and the accompanying drawings. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to explain the technical means of the present invention, the following description will be given by way of specific examples.
Embodiments of the present invention provide an easily-activated hydrogen storage alloy, which has a chemical general formula: ti50-xMxFe50-yNy-(TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80.
Specifically, the easily activatable hydrogen storage alloy of the present invention comprises: a hydrogen storage alloy body and a hydrogen storage material active agent disposed on a surface of the hydrogen storage alloy body,wherein, the chemical general formula of the hydrogen storage alloy main body is as follows: ti50-xMxFe50-yNyThe chemical general formula of the hydrogen storage material active agent is as follows: (TiFe)100-aAa. The hydrogen storage material active agent is arranged on the surface of the hydrogen storage alloy main body, so that a hydrogen passing window is opened for the activation of the hydrogen storage alloy main body, the hydrogen storage material active agent is an intermediate alloy with higher hydrogen absorption activity, and the hydrogen storage material active agent promotes the activation performance of the hydrogen storage alloy main body without sacrificing or extremely sacrificing the hydrogen storage density of the hydrogen storage alloy. In a preferred embodiment, x is more than 0 and less than or equal to 25, and M is one or more of V, Zr, Mg and Al. The selection of x and the type of M within this range can further increase the hydrogen storage performance of the hydrogen storage alloy. In a further preferred embodiment, the weight of the hydrogen storage material active agent is 0.05-1% of the weight of the hydrogen storage alloy main body, and the hydrogen storage performance of the hydrogen storage alloy and the content of the hydrogen storage alloy main body and the hydrogen storage content can be ensured within the weight range.
The invention also provides a manufacturing method of the easily activated hydrogen storage alloy, wherein the manufacturing method of the easily activated hydrogen storage alloy comprises the following steps:
s1: the chemical formula of the preparation is Ti50-xMxFe50-yNyThe main body of the hydrogen storage alloy and the general formula of the preparation is (TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80;
s2: smelting the hydrogen storage alloy main body, and spraying the hydrogen storage material active agent to the surface of the molten hydrogen storage alloy main body to prepare an as-cast hydrogen storage alloy;
s3: and annealing the as-cast hydrogen storage alloy to obtain the easily-activated hydrogen storage alloy.
Specifically, in step S1 described above, raw material preparation is first performed. Surface treatment of titanium, iron and M, N, A raw materialsGrinding with a grinding wheel, or cleaning with weak acid, cleaning with ethanol, drying to remove surface oxide layer and impurities, and processing with Ti50-xMxFe50-yNyThe hydrogen storage alloy is prepared by proportioning the main elements of the hydrogen storage alloy according to the stoichiometric ratio, and uniformly mixing the blocky raw materials and putting the blocky raw materials into a crucible. Will (TiFe)100-aAaThe hydrogen storage alloy activator powder is loaded into the activator tank according to a metered design. Preferably, in step S1), the purity of the selected titanium raw material is more than 98% of sponge titanium or titanium rod, the purity of the selected titanium raw material is 98% of iron rod, and the purity of the rest raw material is higher than 98.5%. Further preferably, in this step, the selected crucible is a three-high graphite crucible or a zirconia ceramic crucible.
Specifically, in step S2), the hydrogen storage alloy body is melted and the activator is added to obtain the as-cast hydrogen storage alloy. Under the protection of vacuum or inert gas, the as-cast hydrogen storage alloy main body is prepared by smelting. Spraying 0.05wt% -1wt% (weight percentage) of hydrogen storage alloy main body active agent powder to the surface of the red molten hydrogen storage alloy in the crucible within 5 seconds-180 seconds after the heating power supply is closed in the last smelting, or spraying 0.05wt% -1wt% (weight percentage) of hydrogen storage alloy active agent powder to the surface of the red molten hydrogen storage alloy main body in the mold within 5 seconds-180 seconds after the mold casting. Preferably, the smelting preparation method in the step S2) is arc smelting, and in order to ensure the uniformity of the alloy structure, the alloy is smelted for 3-5 times in a turning way in the smelting process; alternatively, the smelting preparation method in step S2) is induction smelting.
Specifically, in step S3), annealing heat treatment is performed. Annealing the as-cast hydrogen storage alloy at the temperature of 1000-1400 ℃ for 0.5-4 hours in a vacuum or inert gas protection environment, and cooling to room temperature along with the furnace to obtain the easily activated hydrogen storage alloy.
Preferably, in step S2) and step S3), the vacuum degree of the vacuum environment reaches 5 × 10-3Pa, or 0.05-0.08MPa of inert gas protective environment pressure.
Further, step S4) may be further included, wherein step S4 is: and packaging the hydrogen storage alloy in a vacuum pumping or inert gas filled protection packaging mode.
The invention has the advantages that: (1) compared with ferrotitanium hydrogen storage alloy, the ferrotitanium hydrogen storage alloy is easy to activate, can be activated at one time under the conditions of lower temperature and hydrogen pressure, improves the activation efficiency of the hydrogen storage tank, saves hydrogen, reduces the human input, reduces the energy consumption, shortens the occupied time of production equipment and the like when the hydrogen storage alloy is applied in engineering, and greatly reduces the production cost of the hydrogen storage tank. (2) Compared with alloyed easy-to-activate ferrotitanium hydrogen storage alloy, the material has the advantages of effective hydrogen storage density, hydrogen absorption and desorption rate, pulverization resistance, cycle life and the like, and maintains the original performance advantages. (3) The improved smelting equipment is simple to operate and is suitable for various smelting modes. (4) The hydrogen storage alloy can be easily activated in a block state, so that the processes of crushing and pulverizing the hydrogen storage alloy are omitted, the production efficiency is improved, and the production cost of materials is reduced.
The invention realizes that the preparation equipment of the easily activated ferrotitanium hydrogen storage alloy is improved smelting equipment, and comprises: smelting furnace system, smelting furnace system includes: the device comprises a smelting furnace 1, a mechanical arm 11, an observation window 12, a crucible 13 and a mould 14; a stand-alone unit activator system within a smelting furnace 1, the activator system comprising: the activating agent storage tank 2, the activating agent conveying pipeline 21 and the activating agent injection gun 22 are communicated in sequence; and an independent unit conveying gas system outside the smelting furnace 1, which comprises a tank part 3 for carrying the conveying gas, wherein the tank part 3 is communicated with the active agent storage tank 2 through a pipeline 31. In one embodiment, the transport gas system is an argon gas system, the tank portion 3 carrying the transport gas is an argon gas tank, the pipe 31 is an argon gas pipe 31, and the argon gas pipe 31 is provided with an argon gas valve 32.
The smelting furnace system has the function of completing the smelting of the hydrogen storage alloy main body. The furnace 1 provides a vacuum or argon atmosphere protective environment. The robotic arm 11 controls the position of the active agent spray gun 22 for spraying the active agent. The observation window 12 is used for observing the smelting or casting state of the hydrogen storage alloy, the position state of the injection gun 22 and the injection condition of the active agent. The crucible 13 is a high temperature resistant zirconia ceramic or three-high graphene crucible for holding hydrogen storage alloy. The mold 14 is a rotary water-cooled copper mold for casting of hydrogen storage alloys.
The active agent system functions to store and deliver the active agent. Wherein, the activator storage tank 2 is used for loading hydrogen storage alloy activator, the activator conveying pipeline 21 is a high-temperature resistant plastic hose, the activator injection gun 22 is a red copper necking pipe, and the activator is injected in a directional and positioning way.
The argon system functions to provide high velocity jet motive force for the active agent supply. Wherein, the argon gas tank is a gas source (containing a pressure reducing valve) for storing and providing high-purity argon gas, the argon gas pipeline conveys the high-purity argon gas to the activator storage tank 2, and the argon gas valve 32 controls the supply and the stop of the high-purity argon gas.
In a preferred embodiment, the height of the active agent reservoir 2 is 200-400mm, and the outer diameter of the active agent reservoir 2 is 50-100 mm. Further, the pipe diameter of the active agent injection gun 22 is 5-15mm, and the pipe diameter of the muzzle of the active agent injection gun 22 is 0.1-1 mm.
The easily activatable hydrogen occluding alloy of the present invention will now be described in detail with reference to examples 1 to 5,
examples 1 to 5
The contents of examples 1 to 5 are shown in Table 1.
TABLE 1 representative formulation components for the easy-to-activate TiFe-based Hydrogen storage alloys of the present invention
Further, the method for producing the hydrogen occluding alloy of the present invention will now be described in detail with reference to examples 6 to 7.
Example 6
The easy-to-activate Ti-Fe-based hydrogen storage alloy Ti in the example 1 in the table 150Fe40Mn5Cr5- (TiFe)44Nb56The preparation method comprises the following steps:
a Ti base alloy composition Ti was prepared in accordance with example 150Fe40Mn5Cr5Preparing raw materials. Wherein the titanium material is industrial sea surface titanium with a purity of 98%, the titanium material is cleaned and dried by weak acid, the iron material is pure metal iron rod with a purity of 99%, and the surface of the iron rod is removed by grinding with a grinding wheelThe method comprises the steps of selecting sheet manganese metal with the purity of 99% as a manganese raw material, selecting a chromium metal block with the purity of 98%, crushing the raw materials, mixing and accumulating the crushed raw materials in a three-high graphite crucible of an induction smelting furnace, coating BN on the surface of the induction smelting furnace, and vacuumizing the induction smelting furnace to 5 × 10 DEG-3Pa, induction heating to 1400 ℃, after the raw materials are completely melted, electromagnetically stirring once every 5 minutes, after melting for 20 minutes, closing the heating power supply, pouring the molten materials to a rotary water-cooling copper disk, and after 5 seconds, uniformly spraying 3 times (TiFe) to different areas on a red molten hydrogen storage alloy main body on the water-cooling copper disk44Nb56Active agent (about 0.1 wt%). And opening the furnace to take out the ferrotitanium as-cast hydrogen storage alloy after the as-cast alloy on the water-cooled copper plate is cooled to room temperature. Further, Ti is treated in a vacuum molybdenum wire furnace50Fe40Mn5Cr5-(TiFe)44Nb56Annealing the hydrogen storage alloy with a vacuum degree of 5 × 10-3Pa, heat treatment temperature 1100 deg.C, heat treatment time 30 minutes. Cooling to room temperature along with the furnace to obtain the ferrotitanium hydrogen storage alloy with easy activation and high hydrogen storage density.
Example 7
The easy-to-activate Ti-Fe hydrogen storage alloy Ti in the example 2 of the above Table 138(FeV80)12Fe40Mn10- (TiFe)44Nb56The preparation method comprises the following steps:
a Ti-Fe based hydrogen occluding alloy main body component Ti was formulated as in example 238(FeV80)12Fe40Mn10Preparing raw materials. Wherein the titanium raw material adopts industrial titanium rod with the purity of 98 percent, FeV80The raw material adopts a block material which meets the national standard, the iron raw material adopts a pure metal iron rod with the purity of 99 percent, the 3 raw materials are all polished by a grinding wheel to remove surface oxide skin and impurities, the manganese raw material adopts flaky metal manganese with the purity of 99 percent, the raw materials are cut, mixed and then placed in a specially designed water-cooled copper crucible of an electric arc melting furnace, and the high vacuum is pumped to 5 × 10-3Pa, filling high-purity argon to 0.06MPa, arc melting the alloy raw material in the crucible, closing the arc after the alloy is completely melted, and turning over the crucible after the alloy is cooled and solidifiedRepeatedly melting the alloy ingot for 5 times, and uniformly spraying 5 times (TiFe) to different areas on the red molten hydrogen storage alloy main body after arc quenching is completed for 10 seconds after the last melting44Nb56Active agent (about 0.2 wt%). And opening the furnace to take out the hydrogen storage alloy ingot after the alloy ingot in the crucible is cooled to the room temperature. Further, Ti is treated in a vacuum molybdenum wire furnace38(FeV80)12Fe40Mn10-(TiFe)44Nb56Annealing the hydrogen storage alloy with a vacuum degree of 5 × 10-3Pa, heat treatment temperature 1200 ℃ and heat treatment time 30 minutes. Cooling to room temperature along with the furnace to obtain the ferrotitanium hydrogen storage alloy with easy activation and high hydrogen storage density.
The results of measuring the hydrogen absorption kinetics of the hydrogen occluding alloys obtained in the above examples 6 and 7 using pressure-composition-temperature (PCT) are shown in Table 2 and FIG. 2, the PCT curves for hydrogen desorption of the hydrogen occluding alloy obtained in example 7 under different conditions are shown in FIG. 3, and the metallographic images of the hydrogen occluding alloy obtained in example 7 using a Scanning Electron Microscope (SEM) were obtained.
Comparative example 1
Preferred invention alloy chemical formula Ti of Chinese patent CN99116897.61.2Fe +3.0% Ca alloy of Ti in non-stoichiometric ratio1.2Adding 3.0% Ca into Fe hydrogen storage alloy for alloying, wherein the obtained hydrogen storage alloy can absorb hydrogen when contacting with hydrogen for the first time, but the measured hydrogen storage amount is only 1.7 wt%.
Comparative example 2
Preferred TiFe of Chinese patent CN201610230515.X0.85Mn0.06Co0.08Ce0.02The hydrogen storage alloy is prepared by adopting induction suspension smelting in an argon atmosphere, and the activation needs to be carried out by vacuumizing for 1 hour at the temperature of 80 ℃ and then filling hydrogen for 4MPa, so that the hydrogen storage alloy can be completely activated after repeating for 2 times. The temperature of 25 ℃ is 4MPa of hydrogen charging, and the maximum hydrogen storage density of the alloy is 1.75 wt%.
Table 2 examples 6 and 7 of the present invention are compared with comparative examples 1 and 2 for activation and hydrogen storage performance
It is to be noted that, unless otherwise specified, technical or scientific terms used herein shall have the ordinary meaning as understood by those skilled in the art to which this application belongs.
In the description of the present application, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present application and to simplify the description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the present application.
Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. In the description of the present application, "a plurality" means two or more unless specifically defined otherwise.
In this application, unless expressly stated or limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can include, for example, fixed connections, removable connections, or integral parts; can be mechanically or electrically connected; either directly or indirectly through intervening media, either internally or in any other relationship. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art as appropriate.
In this application, unless expressly stated or limited otherwise, the first feature "on" or "under" the second feature may be directly contacting the first and second features or indirectly contacting the first and second features through intervening media. Also, a first feature "on," "over," and "above" a second feature may be directly or diagonally above the second feature, or may simply indicate that the first feature is at a higher level than the second feature. A first feature being "under," "below," and "beneath" a second feature may be directly under or obliquely under the first feature, or may simply mean that the first feature is at a lesser elevation than the second feature.
The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (9)
1. An easily activatable hydrogen storage alloy having the chemical formula: ti50-xMxFe50-yNy-(TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80; the easily activatable hydrogen storage alloy comprises: the hydrogen storage alloy comprises a hydrogen storage alloy main body and a hydrogen storage material active agent arranged on the surface of the hydrogen storage alloy main body, wherein the chemical general formula of the hydrogen storage alloy main body is as follows: ti50-xMxFe50-yNyThe chemical general formula of the hydrogen storage material active agent is as follows: (TiFe)100-aAa。
2. The easily activatable hydrogen storage alloy of claim 1, wherein x is in the range of 0 < x.ltoreq.25 and M is one or more of V, Zr, Mg, Al.
3. The readily activatable hydrogen storage alloy of claim 1, wherein the hydrogen storage material active agent is present in an amount of from 0.05% to 1% by weight of the hydrogen storage alloy body.
4. A method of producing an easily activatable hydrogen storage alloy as claimed in any one of claims 1 to 3, comprising:
s1: the chemical formula of the preparation is Ti50-xMxFe50-yNyThe main body of the hydrogen storage alloy and the general formula of the preparation is (TiFe)100-aAaWherein M is one or more of Fe, V, Zr, Mg and Al, N is one or more of Cr, Mn, Co and Ni, A is one or more of Li, Nb, La, Ce, Nd, Sm and Y, x is more than or equal to 0 and less than or equal to 25, Y is more than 0 and less than or equal to 25, and a is more than 40 and less than or equal to 80;
s2: smelting the hydrogen storage alloy main body, and spraying the hydrogen storage material active agent to the surface of the molten hydrogen storage alloy main body to prepare an as-cast hydrogen storage alloy;
s3: and annealing the as-cast hydrogen storage alloy to obtain the easily-activated hydrogen storage alloy.
5. The method for producing an easily activatable hydrogen occluding alloy as recited in claim 4, wherein in step S3, said as-cast hydrogen occluding alloy is annealed at a temperature of 1000 ℃ to 1400 ℃ for 0.5h to 4 h.
6. The method for manufacturing an easily activatable hydrogen occluding alloy as claimed in claim 4, wherein the hydrogen occluding alloy main body is melted under vacuum or in an inert gas atmosphere, and the hydrogen occluding material activator is sprayed onto the surface of the molten hydrogen occluding alloy main body within a period of 5 to 180 seconds after the heating power is turned off, or the hydrogen occluding alloy main body in a molten state is sprayed onto the surface of the molten hydrogen occluding alloy main body in a mold within a period of 5 to 180 seconds after the mold casting.
7. The method for producing an easily activatable hydrogen occluding alloy as claimed in claim 6, wherein the weight of the hydrogen occluding material activator is 0.05 to 1% of the weight of the hydrogen occluding alloy main body.
8. A smelting apparatus for producing the activatable hydrogen storage alloy as recited in any one of claims 1 to 3, the smelting apparatus comprising:
the smelting furnace system comprises a smelting furnace, a mechanical arm, a crucible and a mold, wherein the mechanical arm penetrates through the wall of the smelting furnace and extends to the interior of the smelting furnace, and the crucible and the mold are arranged in the smelting furnace;
an activator system within the smelting furnace, comprising: the device comprises an active agent storage tank, an active agent conveying pipeline and an active agent injection gun which are sequentially communicated, wherein the mechanical arm is connected with the active agent injection gun;
the gas conveying system outside the smelting furnace comprises a tank part for bearing the conveying gas, and the tank part is communicated with the active agent storage tank through a pipeline.
9. Smelting apparatus as claimed in claim 8, wherein said activator reservoir has a height of 200-400mm, said activator reservoir has an outer diameter of 50-100mm, said activator injection lance has a bore diameter of 5-15mm, and said activator injection lance has a muzzle bore diameter of 0.1-1 mm.
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| CN113735057A (en) * | 2021-08-31 | 2021-12-03 | 苏州睿分电子科技有限公司 | Activation-free hydrogen storage material and preparation method and device thereof |
| CN114381644B (en) * | 2021-12-10 | 2022-10-21 | 厚普清洁能源(集团)股份有限公司 | Vanadium-titanium-based hydrogen storage alloy powder and preparation method thereof |
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